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US11247510B2 - Metallic or metallized reinforcement, 1HE surface of which is coated with a polybenzoxazine - Google Patents

Metallic or metallized reinforcement, 1HE surface of which is coated with a polybenzoxazine Download PDF

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US11247510B2
US11247510B2 US16/062,990 US201616062990A US11247510B2 US 11247510 B2 US11247510 B2 US 11247510B2 US 201616062990 A US201616062990 A US 201616062990A US 11247510 B2 US11247510 B2 US 11247510B2
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metal
metallized
reinforcer
reinforcer according
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Milan Fedurco
Marco Ribezzo
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Compagnie Generale des Etablissements Michelin SCA
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/10—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
    • C09J181/02—Polythioethers; Polythioether-ethers
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/0666—Reinforcing cords for rubber or plastic articles the wires being characterised by an anti-corrosive or adhesion promoting coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B05D2202/15—Stainless steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
    • B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
    • B60C2009/0014—Surface treatments of steel cords
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles

Definitions

  • thermosetting resins which can be used in particular in adhesive systems intended in particular for the adhesive bonding of metal to rubber.
  • the invention relates more particularly to the metallic or metallized reinforcers coated with polymers that can be used as adhesive layers in metal/rubber composites intended for the manufacture of rubber articles such as pneumatic or non-pneumatic tyres, for motor vehicles.
  • Metal/rubber composites in particular for motor vehicle tyres, are well known. They are usually composed of a matrix made of rubber, generally diene rubber, which can be crosslinked with sulfur, comprising metal reinforcing elements (or “reinforcers”) such as wires, films, tapes or cords made of carbon steel.
  • metal reinforcing elements or “reinforcers”
  • these composites must, in a known way, satisfy a large number of sometimes contradictory technical criteria, such as uniformity, flexibility, flexural strength and compressive strength, tensile strength, wear resistance and corrosion resistance, and must maintain this performance at a very high level for as long as possible.
  • the conventional process for connecting the rubber compositions to carbon steel consists in coating the surface of the steel with brass (copper/zinc alloy), the bonding between the steel and the rubber matrix being provided by sulfurization of the brass during the vulcanization or curing of the rubber.
  • use is generally made, in addition, in these rubber compositions, of organic salts or metal complexes, such as cobalt salts, as adhesion-promoting additives.
  • manufacturers of metal/rubber composites are seeking novel adhesive solutions in order to adhesively bond metal reinforcers to rubber compositions, while overcoming, at least in part, the abovementioned disadvantages.
  • these polymers make it possible very advantageously to adhesively bond the metal to the rubber matrices by subsequently using simple textile adhesives, such as “RFL” (resorcinol/formaldehyde latex) adhesives or other equivalent adhesive compositions, or else directly (that is to say, without employing such adhesives) to these rubber matrices when the latter contain, for example, appropriate functionalized unsaturated elastomers, such as epoxidized elastomers.
  • RRL resorcinol/formaldehyde latex
  • the cobalt salts can in particular be dispensed with in the rubber compositions intended to be connected to brass-coated metal reinforcers.
  • thermosetting type which at ambient temperature has the same adhesive performance, with respect to metal and rubber, as the aforementioned polymers but which has, once thermoset (crosslinked), further improved thermal and chemical stability.
  • its specific microstructure makes it possible very advantageously to adjust the flexibility of the molecule depending on the particular applications targeted.
  • the present invention relates to a metal or metallized reinforcer, at least the surface of which is at least partially metallic, at least said metallic part being coated with a polybenzoxazine comprising at least repeat units comprising at least one unit corresponding to the formulae (I) or (II):
  • the invention relates in particular to such a reinforcer in the form of a wire, film, tape or cord, at least one part of the surface of which is made of steel, in particular of carbon steel, it being possible for said steel to be a bright steel, i.e. uncoated steel, or else to be coated with at least one second metal, referred to as surface metal, the latter being preferentially selected from the group consisting of aluminium, copper, zinc and alloys of at least one of these metals with at least one other metal.
  • the reinforcer of the invention is capable of adhesively bonding matrices of ethylenically unsaturated polymers such as rubber, in particular without the use of cobalt salts in these polymer matrices being necessary.
  • the invention also relates to the use of such a reinforcer for the reinforcement of a rubber article, in particular a pneumatic or non-pneumatic motor vehicle tyre.
  • the invention also relates to any rubber article, in the uncured (non-crosslinked) state or cured (crosslinked) state, in particular any pneumatic or non-pneumatic motor vehicle tyre, which is reinforced by at least one such reinforcer.
  • benzoxazines are compounds of general formula:
  • FIG. 1 a recalls the general principle for the synthesis of a benzoxazine, here starting from (condensation reaction) one molecule of phenol, two molecules of formaldehyde and an amine (R denoting the residue of the amine), with elimination of two molecules of water.
  • FIG. 1 b itself recalls the (ring-opening) mechanism for opening the oxazine ring of such a compound during a heat input (represented by the symbol ⁇ ).
  • benzoxazine compounds or monomers can thus be synthesized using various phenols and amines depending on their types of substituents. These groups of substituents may then provide polymerizable sites and enable the synthesis of various benzoxazine polymers (or polybenzoxazines).
  • Benzoxazines and polybenzoxazines which are derived therefrom are products that are nowadays well known to a person skilled in the art; to cite but a few publication examples, mention may be made of the articles “Poloxazines—New high performance thermosetting resins: synthesis and properties ”; N. N. Ghosh et al., Prog. Polym. Sci. 32 (2007), 1344-1391, or “ Recent Advancement on Polybenzoxazine—A newly Developed High Performance Thermoset ”, Y. Yaggi et al., J. Polym. Sci. Part A: Polym. Chem., Vol. 47 (2009), 5565-5576, and also for example the patents or patent applications U.S. Pat. No. 5,543,516, WO 2013/148408.
  • polybenzoxazines have the remarkable ability, at high temperature (for example typically above 150° C. or even above 200° C. depending on their particular microstructure) to open their oxazine rings and to thus result in thermosetting polyphenolic resin structures.
  • the specific polybenzoxazine suitable for the reinforcer of the invention derives from a benzoxazine (referred to as Monomer M in the present application) of halogenated type that corresponds to the following generic formula (A), Hal representing a (at least one, i.e. one or more) halogen:
  • FIG. 2 gives the general scheme for the synthesis thereof, under heat input and with elimination of water, starting from a halogenated phenol, p-formaldehyde and a diamine.
  • Z 1 represents a bonding group (spacer) that is at least divalent, that is to say that it could comprise more than two covalent bonds, for example three or four covalent bonds.
  • Z 1 is divalent, that is to say comprises only two covalent bonds.
  • Z 1 may be aliphatic, cycloaliphatic or aromatic.
  • This group which may be ethylenically saturated or unsaturated, by definition comprises at least one (i.e. one or more) carbon atom, and optionally at least one (i.e. one or more) heteroatom chosen from O (oxygen), S (sulfur), N (nitrogen) and P (phosphorus).
  • Z 1 represents an aliphatic group comprising from 1 to 20, more preferentially from 1 to 16, in particular from 1 to 12 carbon atoms, or else a cycloaliphatic group comprising from 3 to 20, more preferentially from 3 to 16, in particular from 3 to 12 carbon atoms. More preferentially still, Z1 represents a C 1 -C 20 , preferably C 1 -C 16 , in particular C 1 -C 12 alkylene group.
  • Each benzene ring of the Monomer M bears at least one (i.e. one or more) halogen.
  • one or more hydrogen atoms of at least one or each benzene ring may (optionally) be substituted by various substituents, for example by functional groups capable of promoting the adhesion of the polymer to the metal and/or to the rubber.
  • each benzene ring of the monomer M bears a single halogen (Hal) or at most two, more preferentially one and only one halogen, the latter being more preferentially located in the para position to the oxygen of the oxazine ring.
  • Hal halogen
  • Hal represents bromine
  • FIG. 3 illustrates a possible scheme for the synthesis, starting from a specific diamine of aliphatic type (polyethylene diamine), of a particular halogenated benzoxazine of formula (A-1), this benzoxazine being able to be used as monomer (Monomer denoted by M-1) for the subsequent synthesis of a polybenzoxazine suitable for the reinforcer in accordance with the invention.
  • M-1 halogenated benzoxazine of formula
  • M-1 halogenated benzoxazine of formula
  • Z 1 represents here a —(CH 2 ) x — methylene group in which the symbol “x” represents an integer that preferably varies from 1 to 20, more preferentially from 1 to 16, in particular from 1 to 12.
  • Z 1 represents an aromatic group comprising from 6 to 30, more preferably from 6 to 20, carbon atoms.
  • FIG. 4 illustrates another possible scheme for the synthesis, this time starting from a specific diamine of aromatic type (p-xylylene diamine), of another example of a particular halogenated benzoxazine of formula (A-2), that can be used as monomer (Monomer denoted by M-2) for the subsequent synthesis of another polybenzoxazine suitable for the reinforcer of the invention.
  • FIGS. 5, 6 and 7 illustrate three other possible schemes for the synthesis, always starting from a halogenated phenol and paraformaldehyde on the one hand and, on the other hand, from various specific diamines, all of aliphatic type, of other examples of particular benzoxazines of respective formulae (A-3), (A-4) and (A-5) that can be used as monomers (Monomers respectively denoted by M-3, M-4 and M-5) for the synthesis of polybenzoxazines suitable for the reinforcer of the invention.
  • the repetition of the (polyethylene oxide) [—CH 2 —CH 2 —O—] units on the bonding group Z 1 is capable of resulting in polybenzoxazines of high crystallinity
  • the presence of the (polypropylene oxide) methyl groups on Z 1 makes it possible to reduce the reactivity of the two amine end groups and to result in polybenzoxazines of lower crystallinity.
  • the presence on the spacer Z 1 of the sulfur atom (heteroatom) in the (polyethylene thioether) [—CH 2 —CH 2 —S—] repeat units is capable of further improving the adhesion of the polybenzoxazine to metal.
  • the structure of the Z 1 group of the benzoxazine monomer may be modified considerably with the aim of adjusting the properties of the final polymer. This constitutes a major advantage of the present invention.
  • FIG. 8 illustrates another possible scheme for the synthesis, starting from a halogenated phenol, paraformaldehyde and a specific aliphatic polyamine consisting this time of a triamine, tris(3-aminopropyl)amine, of another example of a particular halogenated (tri)benzoxazine compound of formula (A-6) that can be used as a monomer (Monomer denoted by M-6) for the synthesis of another polybenzoxazine suitable for the reinforcer of the invention.
  • A-6 halogenated (tri)benzoxazine compound of formula (A-6) that can be used as a monomer (Monomer denoted by M-6) for the synthesis of another polybenzoxazine suitable for the reinforcer of the invention.
  • polybenzoxazine (Polymer P) suitable for the reinforcement of the invention therefore has the essential feature of comprising structural repeating units comprising at least one unit corresponding to the formula (I) (before opening of the oxazine rings) or formula (II) (after ring opening) below:
  • a polymer should be understood here as any homopolymer or copolymer, in particular block copolymer, with repeating structural units comprising at least one unit of formula (I) or (II) above; the polymer of the invention may of course comprise both units of formula (I) and units of formula (II).
  • FIG. 9 represents a general scheme for the synthesis, by polycondensation, of such a polybenzoxazine (Polymer P) suitable for the invention, starting from the halogenated benzoxazine of formula (A) from FIG. 2 (Monomer M) and from another monomer, of generic formula denoted by (B), which has the feature of being of aromatic diol or thiol type (generic Monomer denoted by N).
  • one or more hydrogen atoms of at least one or each benzene ring Ar 1 and Ar 2 could (optionally) be substituted by one or more substituents, which are identical or different, for example by functional groups capable of promoting the adhesion of the polymer to the metal and/or to the rubber.
  • the polybenzoxazine “P” from FIG. 9 has also been represented in FIG. 13 , before ( FIG. 13 a , Polymer P) and after ( FIG. 13 b , Polymer P′) the opening of its oxazine rings.
  • FIG. 10 represents a particular scheme for the synthesis of a specific polybenzoxazine (Polymer denoted by P-1) of formula (I-1) suitable for the reinforcer according to the invention, starting from a particular halogenated benzoxazine (Monomer M-7) of formula (A-7) and from another specific monomer (Monomer N-1) of formula (B-1) of sulfur-containing aromatic diol type (4,4′-thiodiphenol).
  • each benzene ring of the monomer M-7 bears one and only one halogen (Hal), more preferentially bromine, this halogen being more particularly located in the para position to the oxygen of the oxazine ring.
  • Hal halogen
  • This polybenzoxazine from FIG. 10 has also been represented in FIG. 14 , before ( FIG. 14 a , Polymer P-1) and after ( FIG. 14 b , Polymer P-1′) the opening of its oxazine rings following a sufficient heat input.
  • the polybenzoxazine of the reinforcement of the invention is characterized by repeat units comprising at least one unit corresponding to the particular formulae (I-1) (before opening of the benzoxazine rings) or (II-1) (after ring opening):
  • FIG. 11 represents another particular scheme for the synthesis of another specific polybenzoxazine (Polymer denoted by P-2) suitable for the invention, of formula (I-2), starting from the preceding specific halogenated benzoxazine (Monomer M-7) and from another specific monomer (Monomer N-2) of formula (B-2), of aromatic thiol type (further bearing an ether function).
  • P-2 polybenzoxazine
  • FIG. 12 represents another particular scheme for the synthesis of another specific polybenzoxazine (Polymer denoted by P-3) suitable for the reinforcer according to invention, of formula (I-3), starting from the preceding specific halogenated benzoxazine (Monomer M-7) and from another specific monomer (Monomer B2) of aromatic thiol type (further bearing a thioether function).
  • each benzene ring of the monomer M-7 bears one and only one halogen (Hal), more preferentially bromine, located more particularly in the para position to the oxygen of the oxazine ring.
  • Hal halogen
  • FIGS. 13 and 14 also represent polybenzoxazines suitable for the reinforcer according to the invention (here respectively denoted by P′ and P-1′) from FIG. 9 and FIG. 10 , once their oxazine rings are open.
  • the polybenzoxazine of the reinforcer of the invention may comprise from ten to several hundred, preferably from 50 to 300 structural units having units of formula (I) and/or (II), in particular structural units as represented as examples in FIGS. 10 to 14 and 17 .
  • the polybenzoxazine of the invention can advantageously be used, as adhesion primer or as sole adhesive layer, for coating the reinforcer of the invention and adhering the latter to rubber.
  • any known adhesive system for example a conventional textile adhesive of “RFL” type comprising at least one diene elastomer such as natural rubber, or any equivalent adhesive known for imparting satisfactory adhesion between rubber and conventional polymers such as polyester or polyamide, such as for example the adhesive compositions described in the patent applications WO 2013/017421, WO 2013/017422, WO 2013/017423, WO 2015/007641, WO 2015/007642.
  • a physical treatment could consist, for example, of a treatment by radiation such as an electron beam, or by plasma;
  • a chemical treatment could consist, for example, of prior passage through a bath of epoxy resin and/or isocyanate compound.
  • connection between the metal reinforcer provided with its polybenzoxazine layer and the rubber layer with which it is in contact will be definitively provided during the final curing (crosslinking) of the rubber article in question.
  • the polybenzoxazine described above can be used very particularly on any type of metal reinforcer, typically of filiform type such as for example a wire, a film (by convention, having a width of greater than 5 cm), a tape (by convention a narrower film having a width at most equal to 5 cm) or a cord made of steel, in particular of carbon steel, intended in particular for reinforcing a matrix of unsaturated rubber such as natural rubber.
  • metal reinforcer typically of filiform type such as for example a wire, a film (by convention, having a width of greater than 5 cm), a tape (by convention a narrower film having a width at most equal to 5 cm) or a cord made of steel, in particular of carbon steel, intended in particular for reinforcing a matrix of unsaturated rubber such as natural rubber.
  • the steel in particular carbon steel, may be a bright steel, i.e. uncoated steel, or else may be coated at least partially with at least one layer (therefore intermediate layer, positioned between steel and polybenzoxazine layer) of a second metal, referred to as surface metal, this surface metal being preferentially selected from the group consisting of aluminium, copper, zinc and alloys of at least one of these metals with at least one other metal (which may or may not belong to this group).
  • the surface metal is brass.
  • the carbon steel is preferentially such as normally used in cords of “steel cord” type for motor vehicle tyres; however, it is, of course, possible to use other steels, for example stainless steels.
  • a carbon steel When a carbon steel is used, its carbon content is preferably between 0.4% and 1.2%, in particular between 0.5% and 1.1%.
  • the invention applies in particular to any steel of the normal tensile (“NT”), high tensile (“HT”), super high tensile (“SHT”) or ultra high tensile (“UHT”) steel cord type.
  • the invention also relates to any rubber article, in the uncured (i.e. non-crosslinked) state or cured (crosslinked) state, in particular any pneumatic or non-pneumatic motor vehicle tyre, comprising a reinforcer according to the invention.
  • This tyre of the invention may be intended for all types of motor vehicles, in particular passenger vehicles or industrial vehicles such as heavy duty vehicles, civil engineering vehicles, and other transport or handling utility vehicles.
  • FIG. 18 represents highly schematically (without being true to a specific scale) a radial section of a tyre in accordance with the invention, for example for a motor vehicle of the passenger vehicle type or for a heavy duty vehicle.
  • This tyre 1 comprises a crown 2 reinforced by a crown reinforcement or belt 6 , two sidewalls 3 and two beads 4 , each of these beads 4 being reinforced with a bead wire 5 .
  • the crown 2 is surmounted by a tread, not represented in this diagrammatic figure.
  • a carcass reinforcement 7 is wound around the two bead wires 5 in each bead 4 , the turn-up 8 of this reinforcement 7 being, for example, positioned towards the outside of the tyre 1 , which is here represented fitted onto its wheel rim 9 .
  • the carcass reinforcement 7 is, in a way known per se, formed, for example, from at least one rubber ply reinforced by reinforcers referred to as “radial” reinforcers, that is to say that these reinforcers are positioned virtually parallel to one another and extend from one bead to the other so as to form an angle of between 80° and 90° with the median circumferential plane (plane perpendicular to the axis of rotation of the tyre which is located halfway between the two beads 4 and passes through the middle of the crown reinforcement 6 ).
  • the belt 6 is, for example, composed, also in a way known per se, of at least two superimposed and crossed rubber plies, known as “working plies” or “triangulation plies”, reinforced with metal reinforcers positioned substantially parallel to one another and inclined with respect to the median circumferential plane, it being possible for these working plies to optionally be combined with other rubber plies and/or fabrics.
  • the primary role of these working plies is to give the pneumatic tyre a high cornering stiffness.
  • the belt 6 can comprise, for example, a rubber ply, referred to as a “hooping ply”, reinforced by reinforcing threads referred to as “circumferential” reinforcing threads, that is to say that these reinforcing threads are positioned virtually parallel to one another and extend substantially circumferentially around the pneumatic tyre so as to form an angle preferably within a range from 0° to 10° with the median circumferential plane.
  • the primary role of these circumferential reinforcing threads is, it should be remembered, to withstand the centrifuging of the crown at high speed.
  • the tyre 1 of the invention has, for example, the essential feature that at least its belt ( 6 ) and/or its carcass reinforcement ( 7 ) comprises a reinforcer in accordance with the invention.
  • it is the bead zone that may be reinforced with such a reinforcer; it is for example the bead wires ( 5 ) that could be formed, in whole or in part, of a such a reinforcer according to the invention.
  • the synthesis is carried out according to the procedure depicted in FIG. 15 , as explained in detail below, starting from three compounds: a halogenated phenol (compound 1; 4-bromophenol; Aldrich product B75808), an aliphatic diamine (compound 2; 1,8-diaminooctane; Aldrich product D22401) and a p-formaldehyde (compound 3; Aldrich 158127 product), in the presence of two solvents (anhydrous toluene and anhydrous ethanol).
  • a halogenated phenol compound 1; 4-bromophenol; Aldrich product B75808
  • an aliphatic diamine compound 2; 1,8-diaminooctane; Aldrich product D22401
  • a p-formaldehyde compound 3; Aldrich 158127 product
  • This oil then undergoes a first purification on an SiO 2 column, with the aid of a diethyl ether/cyclohexane eluent, in a volume ratio of the two solvents that varies from 10:35 (initial) to 10:20 (final).
  • the purified fractions containing the monomer (M-8) are recombined and the solvents are evaporated.
  • a light yellow solid is thus obtained.
  • the latter is placed in methanol (1 g per 80 ml) and heated at reflux (65° C.) for 30 min. The solution is then left to cool to ambient temperature (around 20° C.) for crystallization of the monomer.
  • the solid product obtained is isolated by filtration (Büchner filter). White-coloured crystals are thus obtained, which are dried in a vacuum oven at 50° C., overnight, to eliminate any trace of solvent (reaction yield of around 60%).
  • This synthesis is carried out according to the procedure depicted in the FIG. 17 , as described in detail below, starting from two monomers: the benzoxazine obtained in the preceding step (Monomer M-8) and the sulfur-containing aromatic diol of formula (B-1) (4,4′-thiodiphenol; Monomer N-1) already described in FIG. 10 ; this being in the presence of sodium carbonate (Na 2 CO 3 ; Sigma Aldrich product 13418), and the (anhydrous) solvents DMA (N,N-dimethylacetamide; Sigma Aldrich product 38839) and toluene (Acros Organics product No. 364411000).
  • the two monomers (M-8 and N-1) are dried beforehand under vacuum at 50° C. overnight, and likewise for the sodium carbonate but at a temperature of 150° C.
  • the synthesis is carried out in a 100-ml four-neck round-bottomed flask, equipped with a nitrogen inlet, a thermometer, a magnetic stirrer and a Dean-Stark separator surmounted by a condenser and by a distillation bridge (provided with a heating mantle).
  • the apparatus is dried under vacuum using a hot air gun until the thermometer reaches a temperature of at least 100° C. in the reaction flask. Everything is left to cool to ambient temperature (20° C.), then the apparatus is placed under a stream of nitrogen throughout the synthesis.
  • the distillation bridge of the Dean-Stark apparatus is heated to 110° C. (with the heating mantle) in order to facilitate the azeotropic distillation (water/toluene distillation) carried out for around 90 min.
  • the temperature of the reaction medium is gradually increased, in steps of 10° C. every 30 min, until it reaches 130° C. It is left at this temperature overnight (12 h), then it is left to cool to ambient temperature (20° C.).
  • the reaction mixture is finally poured into 250 ml of distilled water, with vigorous (magnetic bar) stirring; it is left stirring for 30 min (20° C.), then the precipitate thus obtained is isolated by filtration (Büchner funnel) and washed with 100 ml of distilled water; during this washing, in order to extract the carbonate, acid (10% aq. HCl) is added dropwise until a neutral pH is reached.
  • acid (10% aq. HCl) is added dropwise until a neutral pH is reached.
  • the precipitate is once again washed with 100 ml of distilled water, dried under vacuum at 80° C. overnight (around 12 h).
  • This Polymer P-4 in the form of a beige-coloured powder, was also analyzed by DSC (Differential Scanning Calorimetry) between ⁇ 80° C. and +260° C. with a ramp of 10° C./min (Mettler Toledo DSC “822-2” apparatus; nitrogen atmosphere). The analysis showed, in the first pass (between ⁇ 80° C. and +260° C.) an exothermicity (corresponding to the opening of the oxazine rings, and to the crosslinking of the polymer) above 200° C., with a maximum at 240° C. During the second and third DSC passes conducted between ⁇ 80° C. and +260° C., no apparent glass transition (Tg) was visible, which attests to the very high thermal stability of the polymer suitable for the invention.
  • DSC Different Scanning Calorimetry
  • a portion (650 mg) of the Polymer P-4 previously prepared was dissolved in 8 ml of a toluene/DTP (1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; CAS 7226-23-5) mixture (in a 10:1 volume ratio), in order to form a slightly yellow transparent solution, a fraction (0.7 ml) of which was then deposited uniformly on a brass reinforcer (tape) having dimensions of 10 cm ⁇ 2.5 cm and a thickness of 0.3 mm; the assembly was placed in an oven at 175° C. (with air ventilation) for 5 min, then an additional 5 min at 230° C.
  • a brass reinforcer tape
  • the reinforcer of the invention provided at the surface with its thin (5 to 10 ⁇ m thick) layer of polybenzoxazine thus formed, was then subjected to a conventional two-step adhesive coating operation (two bath adhesive coating), firstly by immersion in a first aqueous bath (around 94% water) based on epoxy resin (polyglycerol polyglycidyl ether, around 1%) and on isocyanate compound (caprolactam-blocked isocyanate compound, around 5%), which first adhesive coating step is followed by drying (2 min at 100° C.) then a heat treatment (5 min at 200° C.).
  • the reinforcer thus treated was immersed in a second aqueous bath of RFL adhesive (around 81% by weight of water) based on resorcinol (around 2%), on formol (around 1%) and on a rubber latex (around 16% of NR, SBR and VP-SBR rubbers); finally it was dried in an oven for 2 min at 130° C., then heat treated for 5 min at 200° C.
  • RFL adhesive around 81% by weight of water
  • resorcinol around 2%
  • formol around 17%
  • rubber latex around 16% of NR, SBR and VP-SBR rubbers
  • the brass reinforcer thus coated with the polybenzoxazine film then coated with adhesive was subsequently placed between two layers of conventional rubber composition for a belt reinforcement of a passenger vehicle tyre, based on natural rubber, on carbon black and silica as filler and on a vulcanization system (sulfur and sulfenamide accelerator); this composition being devoid of cobalt salt.
  • the metal/rubber composite test specimen thus prepared was then placed under a press and everything was cured (vulcanized) at 165° C. for 15 min under a pressure of 20 bar.
  • the specific polybenzoxazine described in detail in the present application offers the metal reinforcers of the invention the major advantage of being able subsequently to be adhesively bonded to rubber matrices using simple textile adhesives, such as RFL adhesives, or else directly (that is to say, without employing such adhesives) to these rubber matrices, for example when the latter contain appropriate functionalized unsaturated elastomers, such as epoxidized elastomers.
  • metal reinforcers optionally coated with adhesive metal layers such as brass, and also surrounding rubber matrices devoid of metal salts, in particular of cobalt salts.
  • polybenzoxazines suitable for the reinforcers of the invention have the remarkable ability, at high temperature, to open their oxazine rings and to thus result in a thermosetting polyphenolic resin structure. This gives them a better thermal stability, with no visible phase transition at temperatures above 200° C.
  • their specific microstructure makes it possible, very advantageously, to adjust the flexibility of the molecule depending on the particular applications targeted.

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FR3057872A1 (fr) 2016-10-26 2018-04-27 Compagnie Generale Des Etablissements Michelin Polybenzoxazine utilisable pour le revetement de metal et son collage a du caoutchouc
EP3630736B1 (fr) * 2017-05-24 2022-04-20 Compagnie Générale des Etablissements Michelin Benzoxazine halogénée utilisable pour la synthèse de polybenzoxazine
WO2018215700A1 (fr) 2017-05-24 2018-11-29 Compagnie Generale Des Etablissements Michelin Benzoxazine halogénée utilisable pour la synthèse de polybenzoxazine
FR3067713A1 (fr) 2017-06-14 2018-12-21 Compagnie Generale Des Etablissements Michelin Benzoxazine sulfuree utilisable pour la synthese d'une polybenzoxazine
FR3067646A1 (fr) 2017-06-14 2018-12-21 Compagnie Generale Des Etablissements Michelin Renfort metallique ou metallise dont la surface est revetue d'une polybenzoxazine sulfuree
FR3067714A1 (fr) 2017-06-14 2018-12-21 Compagnie Generale Des Etablissements Michelin Polybenzoxazine sulfuree utilisable pour le revetement de metal et son collage a du caoutchouc
FR3089218A3 (fr) 2018-11-30 2020-06-05 Michelin & Cie Matériau multi-composite à base de composite verre-résine
WO2020109722A1 (fr) 2018-11-30 2020-06-04 Compagnie Generale Des Etablissements Michelin Matériau multi-composite à base de composite verre-résine
WO2020109721A1 (fr) 2018-11-30 2020-06-04 Compagnie Generale Des Etablissements Michelin Matériau multi-composite à base de composite verre-résine
WO2020109723A1 (fr) 2018-11-30 2020-06-04 Compagnie Generale Des Etablissements Michelin Collage d'un monobrin en composite verre-résine à une matrice thermoplastique
JP2023060432A (ja) 2021-10-18 2023-04-28 住友ゴム工業株式会社 空気入りタイヤ

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WO2017103376A1 (fr) 2017-06-22
JP2019507805A (ja) 2019-03-22
EP3390567A1 (fr) 2018-10-24
JP6895970B2 (ja) 2021-06-30
EP3390567B1 (fr) 2020-11-18
KR102562292B1 (ko) 2023-08-02
KR20180095814A (ko) 2018-08-28
FR3045457A1 (fr) 2017-06-23

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